72076-08-5Relevant articles and documents
Fluorinated maleimide-substituted porphyrins and chlorins: Synthesis and characterization
Ol’shevskaya, Valentina A.,Kononova, Elena G.,Zaitsev, Andrei V.
, p. 2704 - 2709 (2019)
Maleimide-containing fluorinated porphyrins and chlorins were prepared based on the reaction of Zn(II) or Ni(II) complexes of 5,10,15,20-tetrakis(4-amino-2,3,5,6-tetrafluorophenyl)porphyrin and chlorin with maleic anhydride. Porphyrin maleimide derivative
A convenient synthesis of pentaporphyrins and supramolecular complexes with a fulleropyrrolidine
Almeida Paz, Filipe A.,Costa, Joana I. T.,Farinha, Andreia S. F.,Tomé, Augusto C.
, (2019)
A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of the absorption and fluorescence spectra were observed upon addition of C60 to the porphyrin derivatives, the addition of PyC60 to the corresponding mono-Zn(II) porphyrins resulted in the formation of Zn(porphyrin)–PyC60 coordination complexes and the binding constants were calculated. Results show that the four free-base porphyrin units in pentaporphyrin 6 have a significant contribution in the stabilization of the 6–PyC60 complex. The crystal and molecular features of the pentaporphyrin Zn5 were unveiled using single-crystal X-ray diffraction studies.
Anomalously selective quenching of S2 fluorescence from upper excited state of zinc 5-(l′-pyrenyl)-10,15,20-triphenylporphyrin derivatives through intramolecular charge transfer state
Hirakawa, Kazutaka,Saito, Keiko,Segawa, Hiroshi
, p. 8852 - 8856 (2009)
Zinc 5-(1′-pyrenyl)-10,15,20-tris(p-methoxyphenyl)porphyrin (ZnP-Py) and zinc 5-(1′-pyrenyl)-10,15,20tris(pentafluorophenyl)porphyrin (ZnFP-Py), in which a pyrenyl group is directly connected at the mesopositions of their corresponding porphyrins, were sy
Design Guidelines to Elongate Spin-Lattice Relaxation Times of Porphyrins with Large Triplet Electron Polarization
Yamauchi, Akio,Fujiwara, Saiya,Nishimura, Koki,Sasaki, Yoichi,Tateishi, Kenichiro,Uesaka, Tomohiro,Kimizuka, Nobuo,Yanai, Nobuhiro
, p. 4334 - 4340 (2021/05/29)
The spin-polarized triplet state generated by light irradiation has potential for applications such as triplet dynamic nuclear polarization (triplet-DNP). Recently, we have reported free-base porphyrins as versatile and biocompatible polarizing agents for triplet-DNP. However, the electron polarization of free-base porphyrins is not very high, and the dilemma is that the high polarization of metalloporphyrins is accompanied by a too short spin-lattice relaxation time to be used for triplet-DNP. We report here that the introduction of electron-withdrawing fluorine groups into Zn porphyrins enables a long enough spin-lattice relaxation time (>1 μs) while maintaining a high polarization (Px:Py:Pz = 0:0:1.0) at room temperature. Interestingly, the spin-lattice relaxation time of Zn porphyrin becomes much longer by introducing fluorine substituents, whereas the spin-lattice relaxation time of free-base porphyrin becomes shorter by the fluorine substitution. Theoretical calculations suggest that this is because the introduction of the electron-withdrawing fluorine substituents reduces the spin density on Zn atoms and weakens the spin-orbit interaction.
Influence of progressive halogenation of Zn(II)-tetraarylporphyrins and their free bases on the structure and spectral-fluorescence properties of tetrapyrrolic macrocycle
Chizhova, Natalya V.,Dmitrieva, Olga A.,Mamardashvili, Nugzar Z.
, (2021/09/22)
Zn(II)-2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin was synthesized by the interaction of Zn(II)-5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin with N-bromosuccinimide in a mixture of chloroform-methanol, chloroform-dimethylformamide and in dimethylformamide. Zn(II)-2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin was formed by the reaction of 2,6-difluoro-substituted Zn(II)-porphyrin with N-chlorosuccinimide in the chloroform-methanol mixture and dimethylformamide. Zn(II)-2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(2,3,4,5,6-pentafluorophenyl) porphyrin was synthesized from Zn(II)-5,10,15,20-tetra-(2,3,4,5,6-pentafluorophenyl)porphyrin with an excess of N-chlorosuccinimide via chlorination in dimethylformamide. The corresponding porphyrin-ligands were obtained by treating halogen-substituted zinc porphyrins with trifluoroacetic acid. The synthesized compounds were characterized by UV–Vis, fluorescence, 1H NMR spectroscopy and mass spectrometry methods. The structures of halogen-substituted porphyrins and their Zn(II) complexes were calculated by the DFT method. The effect of the β-pyrrole halogenation on fluorescence quantum yields of the synthesized compounds was estimated. These halogenated products can be employed for covalent functionalization of the macrocycle pyrrole fragments with the aim of imparting practically important optical, electrochemical and red-ox properties to them.
Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production
Diao, Yingxue,Li, Mu-Qing,Xu, Nanfeng,Xu, Zhengtao,Zhu, Xunjin
supporting information, p. 12643 - 12649 (2020/09/15)
We employ facile aromatic nucleophilic substitution between the mercapto (-SH) and arylfluoro (Ar-F) groups to achieve extensive and robust cross-linking of a coordination host by porphyrin guests that also serve the purpose of versatile postsynthetic fun
Halogenation of Fluoro-Substituted Zinc(II) Tetraphenylporphyrins at the β-Position
Chizhova,Rusanov,Tyurin,Mamardashvili, N. Zh.
, p. 2132 - 2136 (2021/02/09)
Abstract: [2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) was synthesized by reaction of [5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato]zinc(II) with N-bromosuccinimide in chloroform–methanol, chloroform–d
Synthesis of boronated meso-arylporphyrins via copper-catalyzed 1,3-dipolar cycloaddition reaction and their binding ability towards albumin and low density lipoproteins
Egorov, Anton E.,Klimovich, Mikhail A.,Kononova, Elena G.,Koroleva, Olga A.,Kostyukov, Alexey A.,Kuzmin, Vladimir A.,Makarenkov, Anton V.,Markova, Alina A.,Ol'shevskaya, Valentina A.,Zaitsev, Andrei V.
, (2020/04/08)
A series of novel meso- triazoloporphyrin-carborane conjugates was prepared in good yields via the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction of Zn(II) or Pd(II) 5,10,15,20-tetrakis[4-(2-propargyloxy)-2,3,5,6-tetrafluorophenyl]porphyri
Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins
Atoyebi, Adewole O.,Brückner, Christian
supporting information, p. 9631 - 9642 (2019/03/26)
Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.
Transition metal tetrapentafluorophenyl porphyrin catalyzed hydrogen evolution from acetic acid and water
Zhang, Dong-Xu,Yuan, Hui-Qing,Wang, Hua-Hua,Ali, Atif,Wen, Wei-Hong,Xie, An-Na,Zhan, Shu-Zhong,Liu, Hai-Yang
, p. 773 - 782 (2017/09/25)
The performance of Cu (1), Co (2) and Zn (3) complexes of meso-tetrakis(pentafluorophenyl)porphyrin in the electrocatalyzed evolution of hydrogen has been investigated. In acetic acid media, hydrogen evolution turnover frequency (TOF) values for complexes 1, 2 and 3 were 22.1, 19.8 and 18.1?h?1, respectively, at an overpotential of 942?mV versus Ag/AgNO3. In buffer solution at pH 7.0, the corresponding hydrogen evolution TOF values increased dramatically, to 266, 234, 218?h?1 at a similar overpotential of 878?mV versus SHE. The Faradaic yields of 1, 2, and 3 for sustained proton reduction in catalytic experiments at a glassy carbon electrode over 72?h were 89.7, 90.4 and 91.0%, respectively, with no observable catalyst decomposition.
